CN114127226A

CN114127226A - Quantum dot, curable composition including the same, cured layer using the composition, and color filter including the cured layer

Info

Publication number: CN114127226A
Application number: CN202080048082.0A
Authority: CN
Inventors: 姜龙熙; 金钟基; 林知泫; 金东俊; 金美善; 朴民志; 李范珍; 李仁宰; 崔美贞
Original assignee: Samsung SDI Co Ltd
Current assignee: Samsung SDI Co Ltd
Priority date: 2019-10-14
Filing date: 2020-09-18
Publication date: 2022-03-01
Anticipated expiration: 2040-09-18
Also published as: CN114127226B; WO2021075740A1; TW202116721A; JP2022550544A; KR102602724B1; TWI757888B; KR20210044043A; JP7317226B2; US20220213380A1

Abstract

Disclosed are a color filter composed of quantum dots, a curable composition including the quantum dots, a cured layer, and a color filter.

Description

Quantum dot, curable composition including the same, cured layer using the composition, and color filter including the cured layer

Technical Field

The present disclosure relates to a quantum dot, a curable composition including the same, a cured layer produced using the composition, and a color filter including the cured layer.

Background

In the case of general quantum dots, a solvent in which the quantum dots are dispersed is limited due to the surface characteristics having hydrophobicity, and thus, it is difficult to introduce it into a polar system such as an adhesive or a curable monomer.

For example, even in the case of actively studying the quantum dot ink composition, the polarity is relatively low in the initial step, and it can be dispersed in a solvent for a curable composition having high hydrophobicity. Therefore, it is difficult to include 20 wt% or more than 20 wt% of quantum dots based on the total amount of the composition, and thus the light efficiency of the ink cannot be improved beyond a certain level. Although quantum dots are additionally added and dispersed to improve light efficiency, the viscosity exceeds the range capable of Ink-jetting (Ink-jetting) (12 centipoise (cPs)), and may not satisfy the processability.

To obtain a viscosity range capable of ink jetting, a method of reducing the solid content of the ink by dissolving 50% by weight or more than 50% by weight of a solvent based on the total amount of the composition, which also provides a slightly satisfactory result in terms of viscosity. However, it may be considered as a satisfactory result in terms of viscosity, but nozzle drying due to solvent evaporation at the time of jetting (jetting), nozzle clogging, and monolayer reduction with the passage of time after jetting (jetting) may become worse, and it is difficult to control thickness deviation after curing. Therefore, it is difficult to apply it to an actual process.

Therefore, solvent-free quantum dot inks that do not contain solvents are the most desirable form for practical manufacturing processes. Current techniques for applying quantum dots per se to solvent-based compositions are now somewhat limited.

Currently, the most desirable solvent-based composition to be applied to practical processes is quantum dot which is not surface-modified (ligand-substituted) and has a content of 20 to 25 wt% based on the total amount of the solvent-based composition. Therefore, it is difficult to improve light efficiency and absorption rate due to viscosity limitation. Meanwhile, attempts have been made to reduce the quantum dot content and increase the content of a light diffuser (scatterer) in other improvement directions, but this also fails to solve the precipitation problem and the low light efficiency problem.

Disclosure of Invention

Technical problem

An embodiment provides a quantum dot that is surface-modified with a compound having an improved passivation effect, and thus exhibits improved light efficiency.

Another embodiment provides a quantum dot-containing curable composition.

Another embodiment provides a cured layer produced using the curable composition.

Another embodiment provides a color filter including a cured layer.

Technical solution

One embodiment provides a quantum dot surface-modified with a compound represented by chemical formula 1.

[ chemical formula 1]

In the chemical formula 1, the first and second,

l is a divalent moiety derived from an acid dianhydride,

L¹and L²Independently a substituted or unsubstituted C1 to C20 alkylene,

R¹is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, and m is an integer of 1 to 20.

L may be a divalent moiety derived from a compound represented by one of chemical formulas 2-1 to 2-15.

[ chemical formula 2-1]

[ chemical formula 2-2]

[ chemical formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

[ chemical formulas 2 to 6]

[ chemical formulae 2 to 7]

[ chemical formulas 2 to 8]

[ chemical formulas 2 to 9]

[ chemical formulas 2-10]

[ chemical formulas 2 to 11]

[ chemical formulas 2-12]

[ chemical formulas 2-13]

[ chemical formulae 2 to 14]

[ chemical formulas 2 to 15]

L may be represented by one selected from group 1.

[ group 1]

The compound represented by chemical formula 1 may have a weight average molecular weight of less than or equal to 2000 grams per mole (g/mol).

Chemical formula 1 may be represented by one of chemical formulas 1-1 to 1-3.

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

In chemical formulas 1-1 to 1-3,

n is an integer of 1 to 20.

The quantum dots may have a maximum fluorescence emission wavelength of 500 nanometers (nm) to 680 nanometers.

Another embodiment provides a solvent-free curable composition including quantum dots and a polymerizable monomer having a carbon-carbon double bond at a terminal.

The polymerizable monomer in the solvent-free curable composition may have a molecular weight of 220 g/mole to 1,000 g/mole.

The polymerizable monomer in the solvent-free curable composition may be represented by chemical formula 3.

[ chemical formula 3]

In the chemical formula 3, the first and second,

R²and R³Independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L⁷and L⁹Independently is a substituted or unsubstituted C1 to C10 alkylene group, and

L⁸is a substituted or unsubstituted C1 to C10 alkylene or ether (— O-).

The solvent-free curable composition may include 1 to 60 wt% of the quantum dot and 40 to 99 wt% of the polymerizable monomer.

The solvent-free curable composition may further comprise a polymerization initiator, a light diffuser, or a combination thereof.

Another embodiment provides a solvent-based curable composition comprising quantum dots, a binder resin, and a solvent.

The solvent-based curable composition may include 1 to 40 wt% of quantum dots; 1 to 30% by weight of a binder resin; and the balance solvent.

The solvent-based curable composition may further comprise a polymerizable monomer, a polymerization initiator, a light diffuser, or a combination thereof.

Another embodiment provides a color filter including a cured layer.

Other embodiments of the present invention are included in the detailed description below.

Beneficial effect

An embodiment provides a quantum dot surface-modified with a specific compound, which has a very good passivation effect on the quantum dot, can be easily applied to both solvent-based curable compositions and solvent-free curable compositions, and not only has excellent handleability, but also greatly improves the light efficiency of a cured layer produced using the composition, compared to existing quantum dots. In addition, the curable composition including the quantum dot according to the embodiment has improved storage stability and heat resistance.

Detailed Description

Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the invention is not limited thereto, and the invention is defined by the scope of the claims.

In the present specification, when a definition is not otherwise provided, "alkyl" means C1 to C20 alkyl, "alkenyl" means C2 to C20 alkenyl, "cycloalkenyl" means C3 to C20 cycloalkenyl, "heterocycloalkenyl" means C3 to C20 heterocycloalkenyl, "aryl" means C6 to C20 aryl, "arylalkyl" means C6 to C20 arylalkyl, "alkylene" means C1 to C20 alkylene, "arylene" means C6 to C20 arylene, "alkylarylene" means C6 to C20 alkylarylene, "heteroarylene" means C3 to C20 heteroarylene, and "alkyleneoxy" means C1 to C20 alkyleneoxy.

In the present specification, when a specific definition is not otherwise provided, "substituted" means that at least one hydrogen atom is replaced with a substituent selected from: a halogen atom (F, Cl, Br, or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imine group, an azide group, an amidino group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

In the present specification, "hetero" means that at least one hetero atom of N, O, S and P is contained in the chemical formula, when a specific definition is not otherwise provided.

In the present specification, "(meth) acrylate" means both "acrylate" and "methacrylate", and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid", when a specific definition is not otherwise provided.

In the present specification, the term "combination" means mixing or copolymerization when a specific definition is not otherwise provided.

In the present specification, when a definition is not otherwise provided, a hydrogen atom is bonded at a position when a chemical bond is not drawn at the position that should be given in the chemical formula.

In the present specification, the cardol resin refers to a resin containing at least one functional group selected from chemical formulas 4-1 to 4-11 in a backbone (backbone) of the resin.

In addition, in the present specification, "+" refers to a point connected to the same or different atom or chemical formula, when no definition is otherwise provided.

In general, since quantum dots are dispersed in a limited solvent due to hydrophobic surface characteristics, there are many difficulties in introducing quantum dots into a polar system such as a binder resin, a curable monomer, and the like.

For example, a curable composition containing quantum dots, which is actively studied, is prepared by dispersing quantum dots only in a curable composition having relatively low polarity (polarity) and high hydrophobicity (hydrophobicity) in an initial step. Accordingly, since the quantum dots are hardly included in a high content of 20 wt% or more based on the total amount of the composition, the light efficiency of the curable composition may not be improved beyond a certain level, and the quantum dots may be additionally excessively added and dispersed for the purpose of improving the light efficiency, but may not satisfy the processability in the viscosity range (12 centipoise (cPs)) applicable to Ink-jet (Ink-jet).

Further, in order to achieve a viscosity range applicable to inkjet, a method of including a solvent in an amount of 50% by weight or more based on the total amount of the curable composition and thus reducing the solid content therein may be used, and thus the method may bring about excellent viscosity, but has a disadvantage of being difficult to apply to a practical process due to nozzle drying according to solvent evaporation during inkjet, nozzle clogging, a single film thickness reduction with the passage of time after inkjet, and a severe thickness deviation after curing.

Therefore, in view of solvent-free compositions being a suitable development approach for practical processes, quantum dot curable compositions have limitations for application of current quantum dots.

The quantum dots not surface-modified (e.g., ligand-substituted) are contained in a small amount of 20 to 25 wt% based on the total amount of the curable composition reported so far, and thus it is difficult to improve light efficiency and absorption rate due to viscosity limitation. Furthermore, another development approach is to reduce the content of quantum dots and increase e.g. TiO₂The method of isophotodiffuser content also does not improve the precipitation problem or low light efficiency.

Conventional solvent-based curable compositions containing quantum dots may cause nozzle clogging due to drying of the solvent in the nozzle during ink jetting as described above, fail to maintain a target pixel thickness due to evaporation of the ink in the inkjet pixel, and thus fail to ensure inkjet processability.

Furthermore, in order to form a layer having a predetermined thickness by post baking (or otherwise thermally curing) after forming a thin film in a pixel, a pinning (pinning) point (maximum height at which bubbles do not collapse) should be formed by jetting a large amount of ink at a position far higher than the height of the pixel, which is practically impossible, and furthermore, a processable solvent should have a surface tension of approximately 40 dyne/cm (dyne/cm), which is rarely likely to occur.

Accordingly, the present inventors have long studied and disclosed a method for surface-modifying quantum dots with ligands that do not have a thiol group and thus have a structure different from that of ligands conventionally used for surface-modifying quantum dots, but include a divalent moiety derived from dianhydride, in order to prevent the optical properties of quantum dots from being deteriorated, and at the same time, greatly improve the storage stability and heat resistance of the curable composition containing quantum dots.

For example, the ligand may be represented by chemical formula 1.

[ chemical formula 1]

In the chemical formula 1, the first and second,

l is a divalent moiety derived from an acid dianhydride,

L¹and L²Independently a substituted or unsubstituted C1 to C20 alkylene,

R¹is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, and

m is an integer of 1 to 20.

The compound represented by chemical formula 1 is a ligand having a structure different from that of a thiol-based compound conventionally used as a material for surface modification of quantum dots and derived from acid dianhydride, and when used for surface modification of quantum dots, the surface-modified quantum dots can greatly improve the light efficiency of a cured layer formed of a composition containing the quantum dots, and in addition, can enhance the storage stability and heat resistance of the composition.

For example, L may be a divalent moiety derived from a compound represented by one of chemical formulas 2-1 to 2-15, but is not limited thereto.

[ chemical formula 2-1]

[ chemical formula 2-2]

[ chemical formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

[ chemical formulas 2 to 6]

[ chemical formulae 2 to 7]

[ chemical formulas 2 to 8]

[ chemical formulas 2 to 9]

[ chemical formulas 2-10]

[ chemical formulas 2 to 11]

[ chemical formulas 2-12]

[ chemical formulas 2-13]

[ chemical formulae 2 to 14]

[ chemical formulas 2 to 15]

For example, L may be represented by one selected from group 1, but is not limited thereto.

[ group 1]

The compound represented by chemical formula 1 may have a weight average molecular weight of less than or equal to 2000 g/mole, for example, 400 g/mole to 2000 g/mole. When the weight average molecular weight of the compound represented by chemical formula 1 is within the above range, the viscosity of the curable composition including the quantum dot surface-modified with the compound may be kept low, which may be advantageous for inkjet.

For example, chemical formula 1 may be represented by one of chemical formula 1-1 to chemical formula 1-3, but is not limited thereto.

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

In chemical formulas 1-1 to 1-3,

n is an integer of 1 to 20.

The quantum dots may have a maximum fluorescence emission wavelength of 500 to 680 nanometers.

A curable composition according to another embodiment includes a quantum dot surface-modified with a compound represented by chemical formula 1.

To date, curable compositions (inks) containing quantum dots may have been developed towards specialized monomers with good compatibility with quantum dots, and in addition they have been commercialized.

On the other hand, since a generally and widely used polymerizable monomer, an-ene (-ene) based monomer (including a vinyl based monomer, an acrylate based monomer, a methacrylate based monomer, etc., which includes a monofunctional monomer or a polyfunctional monomer) has low compatibility with the quantum dot and is limited in dispersibility of the quantum dot, it is substantially difficult to effectively apply it to various developments of a curable composition containing the quantum dot. Most importantly, the-ene-based monomers do not exhibit high concentration quantum dot dispersibility and thus are difficult to apply to quantum dot-containing curable compositions.

Due to such a disadvantage, a curable composition containing quantum dots has been developed to have a composition containing a considerable amount (50 wt% or more) of a solvent, but inkjet (Ink) processability may be deteriorated when the solvent content is increased. Therefore, in order to satisfy inkjet (Ink jetting) processability, there is an increasing demand for solvent-free curable compositions.

The present invention provides a solvent-free curable composition with increased demand by: the polymerizable monomer including the compound having a carbon-carbon double bond at the terminal and the quantum dot surface-modified by the compound represented by chemical formula 1 or chemical formula 2 are used to increase the affinity of the quantum dot for the curable composition, and thus a high-concentration dispersion of the quantum dot is obtained even in a solvent-free system (solvent-free system), and in addition, passivation (deactivation) that does not deteriorate the intrinsic optical properties of the quantum dot is achieved.

Hereinafter, each component constituting the solvent-free curable composition is described in detail.

Quantum dots

The quantum dot included in the solvent-free curable composition includes a quantum dot surface-modified with a compound represented by chemical formula 1.

For example, the quantum dots absorb light in a wavelength region of 360 nm to 780 nm, e.g., 400 nm to 780 nm, and emit fluorescence in a wavelength region of 500 nm to 700 nm, e.g., 500 nm to 580 nm or emit fluorescence in a wavelength region of 600 nm to 680 nm. That is, the quantum dot may have a maximum fluorescence emission wavelength (fluorescence λ) at 500 nm to 680 nm_em)。

The quantum dots can independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, such as 20 nm to 50 nm. When the quantum dot has a full width at half maximum (FWHM) of the range, color reproducibility increases due to high color purity when used as a color material in a color filter.

The quantum dots may be independently organic materials, inorganic materials, or a hybrid (mixture) of organic and inorganic materials.

The quantum dot may be independently composed of a core and a shell surrounding the core, and the core and the shell may independently have a structure of a core, a core/shell, a core/first shell/second shell, an alloy/shell, etc., composed of groups II-IV, III-V, etc., but is not limited thereto.

For example, the core may include at least one material selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof, but is not necessarily limited thereto. The shell surrounding the core may include at least one material selected from CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.

In the embodiment, since the attention to the environment has been greatly increased worldwide recently and the constraint of toxic materials has been strengthened, a cadmium-free luminescent material (InP/ZnS, InP/ZnSe/ZnS, etc.) having a cadmium-based core, which is slightly low in quantum efficiency (quantum yield), but is environmentally friendly, is used instead of the luminescent material having a cadmium-based core, but is not necessarily limited thereto.

In the case of a core/shell structured quantum dot, the overall size (average particle diameter) including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.

For example, the quantum dots may independently comprise red quantum dots, green quantum dots, or a combination thereof. The red quantum dots may independently have an average particle diameter of 10 to 15 nanometers. The green quantum dots may independently have an average particle diameter of 5 nm to 8 nm.

On the other hand, to achieve dispersion stability of the quantum dots, the solvent-free curable composition according to the embodiment may further include a dispersant. The dispersant contributes to uniform dispersibility of the light conversion material such as quantum dots in the solvent-free curable composition, and may include a nonionic dispersant, an anionic dispersant, or a cationic dispersant. Specifically, the dispersant may be polyalkylene glycol or an ester thereof, polyalkylene oxide, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonic acid ester, carboxylic acid salt, alkylamide alkylene oxide addition product, alkylamine, or the like, and it may be used alone or in a mixture of two or more. The dispersant may be used in an amount of 0.1 to 100 wt%, for example, 10 to 20 wt%, based on the solid content of the light conversion material (e.g., quantum dot).

The quantum dots surface-modified with chemical formula 1 may be included in an amount of 1 to 60 wt%, for example, 3 to 50 wt%, based on the total amount of the solvent-free curable composition. When the surface-modified quantum dot is included in the range, the light conversion rate may be improved, and the pattern characteristic and the developing characteristic are not disturbed, so that it may have excellent processability.

Polymerizable monomer having carbon-carbon double bond at terminal

The monomer having a carbon-carbon double bond at the terminal should be contained in an amount of 40 to 99 wt%, for example, 50 to 97 wt%, based on the total amount of the solvent-free curable composition. When the monomer having a carbon-carbon double bond at the terminal is included in the range, a solvent-free curable composition having a viscosity capable of ink jetting may be prepared, and the quantum dots in the prepared solvent-free curable composition may have improved dispersibility, thereby improving optical properties.

For example, the monomer having a carbon-carbon double bond at the terminal may have a molecular weight of 220 g/mole (g/mol) to 1,000 g/mole. When the monomer having a carbon-carbon double bond at the terminal has a molecular weight within the range, ink jetting can be advantageously performed because it does not increase the viscosity of the composition and does not hinder the optical properties of the quantum dot.

For example, the monomer having a carbon-carbon double bond at the terminal may be represented by chemical formula 3, but is not necessarily limited thereto.

[ chemical formula 3]

In the chemical formula 3, the first and second,

L⁸is a substituted or unsubstituted C1 to C10 alkylene or ether (— O-).

For example, the monomer having a carbon-carbon double bond at the terminal may be represented by chemical formula 3-1 or 3-2, but is not necessarily limited thereto.

[ chemical formula 3-1]

[ chemical formula 3-2]

For example, the monomer having a carbon-carbon double bond at the terminal may include ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or a combination thereof.

Further, a monomer commonly used for conventional thermosetting or photocurable compositions may be further contained together with a monomer having a carbon-carbon double bond at the terminal. For example, the monomer also includes oxetane compounds such as bis [ 1-ethyl (3-oxetanyl) ] methyl ether and the like.

Polymerization initiator

The solvent-free curable composition according to the embodiment may further include a polymerization initiator, such as a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

The photopolymerization initiator is an initiator commonly used for photosensitive resin compositions, and examples thereof include acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, and amino ketone-based compounds, but not necessarily limited thereto.

Examples of the acetophenone-based compound may be 2,2' -diethoxyacetophenone, 2' -dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2' -dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like.

Examples of the benzophenone-based compound may be benzophenone, benzoyl benzoate, benzoylmethyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -dimethylaminobenzophenone, 4' -dichlorobenzophenone, 3' -dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

Examples of the triazine-based compound may be 2,4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (3',4' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4' -methoxynaphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-biphenyl-4, 6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphthol 1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol 1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2-4-bis (trichloromethyl) -6-piperonyl-s-triazine, 2-4-bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine and the like.

Examples of the oxime-based compound may be O-acyloxime-based compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione, 1- (O-acetyloxime) -1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone, O-ethoxycarbonyl- α -oxyamino-1-phenylpropan-1-one, and the like. Specific examples of the O-acyloxime-based compound may be 1, 2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 1- (4-phenylthiophenyl) -butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-phenylthiophenyl) -octane-1, 2-dione-2-oxime-O-benzoate, 1- (4-phenylthiophenyl) -octan-1-one oxime-O-acetate, 1- (4-phenylthiophenyl) -butane-1-one oxime-O-acetate, and the like.

Examples of the amino ketone compound include 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (2-Benzyl-2-dimethyllamino-1- (4-morpholinophenyl) -butanone-1), and the like.

The photopolymerization initiator may further contain a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a bisimidazole-based compound, and the like, in addition to the above-mentioned compounds.

The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming excited and then transmitting its energy.

Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

Examples of the thermal polymerization initiator may be peroxides, specifically benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-sec-butyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, hydroperoxides (e.g., tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2-azo-bis (isobutyronitrile), tert-butyl perbenzoate, and the like, such as 2,2' -azobis-2-methylpropionitrile, but are not necessarily limited thereto, and any one known in the art may be used.

The polymerization initiator may be included in an amount of 0.1 to 5 wt%, for example, 1 to 4 wt%, based on the total amount of the solvent-free curable composition. When the polymerization initiator is included within the range, excellent reliability may be obtained due to sufficient curing during exposure or thermal curing, and deterioration of transmittance due to a non-reactive initiator is prevented, thereby preventing deterioration of optical properties of the quantum dot.

Light diffusing agent (or light diffusing agent dispersion)

The solvent-free curable composition according to the embodiment may further include a light diffuser.

For example, the light diffuser may include barium sulfate (BaSO)₄) Calcium carbonate (CaCO)₃) Titanium dioxide (TiO)₂) Zirconium oxide (ZrO)₂) Or a combination thereof.

The light diffusing agent may reflect unabsorbed light in the aforementioned quantum dots and allow the quantum dots to absorb the reflected light again. That is, the light diffuser may increase the amount of light absorbed by the quantum dots and improve the light conversion efficiency of the curable composition.

The light diffuser may have an average particle diameter (D) of 150 to 250 nm, and specifically 180 to 230 nm₅₀). When the average particle diameter of the light diffuser is within the range, it may have a better light diffusing effect and improve light conversion efficiency.

The light diffuser may be included in an amount of 1 to 20 wt%, for example, 5 to 10 wt%, based on the total amount of the solvent-free curable composition. When the light diffuser is included in an amount of less than 1 wt% based on the total amount of the solvent-free curable composition, it is difficult to expect a light conversion efficiency improving effect due to the use of the light diffuser, whereas when the light diffuser is included in an amount of more than 20 wt%, there is a possibility that the quantum dot may be precipitated.

Other additives

To achieve stability and dispersion improvement of the quantum dots, the solvent-free curable composition according to the embodiment may further include a polymerization inhibitor.

The polymerization inhibitor may include hydroquinone-based compounds, catechol-based compounds, or a combination thereof, but is not necessarily limited thereto. When the solvent-free curable composition according to the embodiment further includes a hydroquinone-based compound, a catechol-based compound, or a combination thereof, room temperature crosslinking during exposure after coating the solvent-free curable composition may be prevented.

For example, the hydroquinone-based compound, the catechol-based compound, or the combination thereof may be hydroquinone, methylhydroquinone, methoxyhydroquinone, tributylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2, 5-bis (1, 1-dimethylbutyl) hydroquinone, 2, 5-bis (1,1,3, 3-tetramethylbutyl) hydroquinone, catechol, tert-butylcatechol, 4-methoxycatechol, gallophenol, 2, 6-di-tert-butyl-4-methylphenol, 2-naphthol, Tris (N-hydroxy-N-nitrosophenylamino-O, O ') aluminum (Tris (N-hydroxy-N-nitrosophenylamino-O, O') aluminum), or a combination thereof, but is not necessarily limited thereto.

The hydroquinone-based compound, the catechol-based compound, or a combination thereof may be used in the form of a dispersion. The polymerization inhibitor may be included in the form of a dispersion in an amount of 0.001 to 3% by weight, for example, 0.1 to 2% by weight, based on the total amount of the solvent-free curable composition. When the polymerization inhibitor is included within the range, the time lapse at room temperature can be solved, and at the same time, the sensitivity deterioration and the surface delamination phenomenon can be prevented.

Further, the solvent-free curable composition according to the embodiment may further include malonic acid; 3-amino-1, 2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof, to improve heat resistance and reliability.

For example, the solvent-free curable composition according to the embodiment may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, or the like, to improve the close contact property with the substrate.

Examples of the silane-based coupling agent may be trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta-epoxycyclohexyl) ethyltrimethoxysilane, etc., and these coupling agents may be used alone or in a mixture of two or more.

The silane-based coupling agent may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the solvent-free curable composition. When the silane-based coupling agent is contained within the range, the close contact property, the storage ability, and the like are improved.

In addition, the solvent-free curable composition may optionally further comprise a surfactant (e.g., a fluorine-based surfactant) to improve coating properties and suppress the generation of spots, i.e., to improve leveling (leveling) performance.

The fluorine-based surfactant may have a low weight average molecular weight of 4,000 g/mole to 10,000 g/mole, and specifically 6,000 g/mole to 10,000 g/mole. In addition, the fluorine-based surfactant may have a surface tension of 18 milli-newtons per meter (mN/m) to 23 milli-newtons per meter (measured in a 0.1% Polyethylene Glycol Monomethyl Ether Acetate (PGMEA) solution). When the fluorine-based surfactant has a weight average molecular weight and a surface tension within the ranges, leveling performance may be further improved, and when slit coating (slit coating) is applied as high speed coating (high speed coating), excellent characteristics may be provided, since film defects may be less generated by preventing generation of spots and suppressing generation of vapor during high speed coating.

An example of the fluorine-based surfactant may be

And

(BM chemistry)Company (BM Chemie Inc.); meijia Method (MEGAFACE) F

F

F

And F

(Dainippon Ink chemical Co., Ltd. (Dainippon Ink Kagaku Kogyo Co., Ltd.)); florade (FULORAD)

Florad

Florad

And Florad

(Sumitomo 3M Co., Ltd.); shafulon (SURFLON)

Shafulong (a medicine for treating diabetes)

Shafulong (a medicine for treating diabetes)

Shafulong (a medicine for treating diabetes)

And saflufon

(Asahi glass Co., Ltd.) (ASAHI Glass co., Ltd.)); and

and

etc. (Toray Silicone co., Ltd.)); f-482, F-484, F-478, F-554, and the like, available from Dainippon ink chemical Co., Ltd.

Further, the solvent-free curable composition according to the embodiment may further include a silicone-based surfactant in addition to the fluorine-based surfactant. Specific examples of the silicone-based surfactant may be TSF400, TSF401, TSF410, TSF4440, and the like, of Toshiba silicone co.

The surfactant may be included in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 2 parts by weight, based on 100 parts by weight of the solvent-free curable composition. When the surfactant is contained in the range, foreign substances are less generated in the sprayed composition.

In addition, the solvent-free curable composition according to the embodiment may further include predetermined amounts of other additives, such as an antioxidant, a stabilizer, and the like, unless the properties are deteriorated.

For example, the curable composition may include a solvent-based curable composition including quantum dots surface-modified by chemical formula 1, a binder resin, and a solvent, in addition to the solvent-free curable composition. Herein, the surface-modified quantum dots may be included in an amount of 1 to 40 wt%, based on the total weight of the solvent-based curable composition. When the surface-modified quantum dots are included in the content range based on the total amount of the solvent-type curable composition, it may be advantageous in terms of handleability.

Hereinafter, each component constituting the solvent-type curable composition is described in detail.

Adhesive resin

The adhesive resin may include an acrylic resin, a cardo resin, an epoxy resin, or a combination thereof.

The acrylic resin may be a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin comprising at least one acrylic repeating unit.

The first ethylenically unsaturated monomer may be an ethylenically unsaturated monomer including at least one carboxyl group, and examples of the monomer may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5 to 50 wt% (e.g., 10 to 40 wt%), based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α -methylstyrene, vinyltoluene, vinylbenzyl methyl ether, or the like; unsaturated carboxylic acid ester compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and the like; unsaturated aminoalkyl carboxylate compounds such as 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, and the like; vinyl carboxylate compounds such as vinyl acetate, vinyl benzoate and the like; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate and the like; vinyl cyanide compounds such as (meth) acrylonitrile and the like; unsaturated amide compounds such as (meth) acrylamide and the like; and the like, and the second ethylenically unsaturated monomer may be used alone or in a mixture of two or more.

Specific examples of the acrylic binder resin may be, but are not limited to, polymethyl methacrylate, a (meth) acrylic acid/benzyl methacrylate copolymer, a (meth) acrylic acid/benzyl methacrylate/styrene copolymer, a (meth) acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer, a (meth) acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like, and these may be used alone or in a mixture of two or more.

The weight average molecular weight of the acrylic binder resin may be from 5,000 g/mole to 15,000 g/mole. When the weight average molecular weight of the acrylic binder resin is within the range, close contact property with the substrate, physical and chemical properties are improved, and viscosity is appropriate.

The carduon resin may include a repeating unit represented by chemical formula 4.

[ chemical formula 4]

In the chemical formula 4, the first and second organic solvents,

R³¹and R³²Independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R³³and R³⁴Independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z¹is a single bond, O, CO, SO₂、CR³⁵R³⁶、SiR³⁷R³⁸(wherein, R³⁵To R³⁸Independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or a linking group represented by chemical formula 4-1 to chemical formula 4-11,

[ chemical formula 4-1]

[ chemical formula 4-2]

[ chemical formulas 4-3]

[ chemical formulas 4-4]

[ chemical formulas 4-5]

Wherein, in chemical formulas 4 to 5,

R^ais hydrogen atom, ethyl, C₂H₄Cl、C₂H₄OH、CH₂CH＝CH₂Or a phenyl group,

[ chemical formulas 4-6]

[ chemical formulas 4 to 7]

[ chemical formulas 4 to 8]

[ chemical formulas 4 to 9]

[ chemical formulas 4-10]

[ chemical formulas 4-11]

Z²Is an anhydride moiety, and

t1 and t2 are independently integers in the range of 0 to 4.

The weight average molecular weight of the cardol multi-component binder resin may be 500 g/mole to 50,000 g/mole, for example 1,000 g/mole to 30,000 g/mole. When the weight average molecular weight of the carden multisystem binder resin is within the range, a satisfactory pattern can be formed without residue during production of the cured layer and without loss of film thickness during development of the solvent-type curable composition.

The carduon-series adhesive resin may include a functional group represented by chemical formula 5 at least one of both ends.

[ chemical formula 5]

In the chemical formula 5, the first and second organic solvents,

Z³represented by chemical formula 5-1 to chemical formula 5-7.

[ chemical formula 5-1]

In chemical formula 5-1, R^bAnd R^cIndependently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.

[ chemical formula 5-2]

[ chemical formulas 5-3]

[ chemical formulas 5-4]

[ chemical formulas 5 to 5]

In chemical formula 5-5, R^dO, S, NH, substituted or unsubstituted C1 to C20 alkylene, C1 to C20 alkylamino, or C2 to C20 alkenylamino.

[ chemical formulas 5 to 6]

[ chemical formulas 5 to 7]

Cardol resins can be prepared, for example, by mixing at least two of the following compounds: fluorene-containing compounds such as 9, 9-bis (4-oxacyclopropylmethoxyphenyl) fluorene; acid anhydride compounds such as pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic dianhydride, and tetrahydrophthalic anhydride; glycol compounds such as ethylene glycol, propylene glycol and polyethylene glycol; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; solvent-based compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidinone; phosphorus compounds such as triphenylphosphine, etc.; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, or benzyltriethylammonium chloride.

When the binder resin is a cardmultisine resin, a solvent-type curable composition, particularly a photosensitive resin composition, comprising the cardmultisine resin has excellent developability and sensitivity during photocuring and thus has fine pattern formation ability.

The acid value of the acrylic resin may be 80 mg KOH/g (mgKOH/g) to 130 mg KOH/g. When the acid value of the acrylic resin is within the range, excellent pixel resolution can be obtained.

The epoxy resin may be a thermally polymerizable monomer (monomer) or oligomer (oligomer), and may include compounds having carbon-carbon unsaturated bonds and carbon-carbon cyclic bonds.

The epoxy resin may further include bisphenol a epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cyclic aliphatic epoxy resin, and aliphatic polyglycidyl ether, but is not necessarily limited thereto.

As commercially available products of the compounds, there may be mentioned bisphenyl Epoxy resins, such as YX4000, YX4000H, YL6121H, YL6640 or YL6677 of Yuka Shell Epoxy co, Ltd; cresol novolac epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 from Nippon Kayaku Co. Ltd., (Nostoc corporation, Japan), and Epicot (EPIKOTE)180S75 from Eja shell epoxy Co., Ltd.); bisphenol a epoxy resins such as epicocote 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 by yu jia shell epoxy limited; bisphenol F epoxy resins such as epidett 807 and 834 from yu jia shell epoxy limited; phenol novolac epoxy resins, such as EPPN 152, 154 or 157H65 from yu jia shell epoxy and EPPN 201, 202 from japan chemicals co; cyclic aliphatic epoxy resins, such as CY175, CY177 and CY179 from Ciba-Geigy A.GCorp., Inc., ERL-4234, ERL-4299, ERL-4221 and ERL-4206 from Ciba-Geigy A.G, eleydine (Showdyne)509 from U.C.C., Showa Denko K.K, Elida (Araldite) CY-182, CY-184 and CY-192 from Ciba-Geigy A.G, Epicolon (EPICLON)200 and 400 from Daippon Ink chemical Co., Ltd. (Daippon Ink and Chemicals Inc.), Epicotte (EPICOTE) 871 and 400 from Eicokaki Kagaku (Eicoku) 871 and EP 872, EP 5661 and EP 561032 from Seinese Coating Corporation (Annese Coating H. 60, EP 5661 and EP 561032; aliphatic polyglycidyl ethers such as EPIOL TMP from Egyaku Shell epoxy company, Elpidet 190P and 191P, EPOLITE (EPOLITE)100MF from Kyoeisha Yushi Kagaku Kogyo Co., Ltd., Japan, and EPIOL TMP from Nihon Yushi K.K.

The binder resin may be included in an amount of 1 to 30 wt% based on the total weight of the solvent-based curable composition.

Solvent(s)

The solvent may, for example, include alcohols, such as methanol, ethanol, and the like; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether and the like; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, and the like; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, 2-heptanone, and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, and the like; lactates such as methyl lactate, ethyl lactate, and the like; alkyl glycolates such as methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkoxyalkyl acetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like; alkyl 3-hydroxypropionates such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate and the like; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-hydroxypropionates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, and the like; alkyl 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropionates such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and the like; alkyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, 2-hydroxy-3-methyl butyrate, and the like; or ketoacid esters such as ethyl pyruvate, etc., and further, may be N-methylformamide, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate (phenyl cellosolve acetate), etc., but is not limited thereto.

For example, the solvent may desirably be a glycol ether, such as ethylene glycol monoethyl ether, or the like; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate and the like; esters such as 2-hydroxyethyl propionate and the like; carbitols such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like; alcohols, such as ethanol, and the like, or combinations thereof.

For example, the solvent may be a polar solvent including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ -butyrolactone, or a combination thereof.

The balance, e.g., 30 to 80 wt%, e.g., 35 to 70 wt%, of the solvent may be included based on the total amount of the solvent-based curable composition. When the solvent is in the range, the solvent-based curable composition has an appropriate viscosity, and thus may have excellent coating properties when coated in a large area by spin coating and slit coating.

For example, the solvent-type curable composition may further contain at least one of a polymerizable monomer having a carbon-carbon double bond at the terminal, a polymerization initiator, a light diffuser, and other additives, and the detailed composition or amount thereof is the same as described above.

For example, the solvent-based curable composition may be a photosensitive resin composition. In this case, the solvent-type curable composition may include a photopolymerization initiator as a polymerization initiator.

Another embodiment provides a cured layer produced using the above solvent-free curable composition and solvent-based curable composition, a color filter including the cured layer, and a display device including the color filter.

One method of producing a cured layer may include: coating the above solvent-free curable composition and solvent-based curable composition on a substrate using an inkjet spray method to form a pattern (S1); and curing the pattern (S2).

(S1) Pattern formation

It may be desirable to coat the solvent-free curable composition on the substrate to 0.5 to 20 micrometers in an inkjet spray method. The inkjet ejection method may form a pattern by ejecting a single color per nozzle and thus repeatedly ejecting as many times as the required number of colors, but a pattern may be formed by simultaneously ejecting the required number of colors per inkjet nozzle to reduce the process.

(S2) curing

The obtained pattern is cured to obtain pixels. Herein, the curing method may be a thermal curing or photo curing process. The thermal curing process may be performed at greater than or equal to 100 ℃, desirably in the range of 100 ℃ to 300 ℃, and more desirably in the range of 160 ℃ to 250 ℃. The photo-curing process may include irradiating actinic rays, such as ultraviolet rays of 190 nm to 450 nm, such as 200 nm to 500 nm. Irradiation is performed by using a light source such as a mercury lamp, a metal halide lamp, an argon laser, or the like having a low pressure, a high pressure, or an ultrahigh pressure. X-rays, electron beams, etc. may be used as necessary.

Other methods of producing a cured layer may include producing a cured layer by the following photolithography method using the aforementioned solvent-free curable composition or solvent-based curable composition.

(1) Coating and film formation

The aforementioned curable resin composition is coated on a substrate subjected to a predetermined pretreatment to have a desired thickness, for example, a thickness in the range of 2 to 10 μm, using a spin coating or slit coating method, a roll coating method, a screen printing method, a coater method, or the like. Then, the coated substrate is heated at a temperature of 70 ℃ to 90 ℃ for 1 minute to 10 minutes to remove the solvent and form a film.

(2) Exposure method

After the mask having a predetermined shape is set, the resulting film is irradiated with actinic rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm to form a desired pattern. The irradiation is performed using a light source such as a mercury lamp, a metal halide lamp, an argon laser, or the like having a low pressure, a high pressure, or an ultrahigh pressure. X-rays, electron beams, etc. may be used as necessary.

When a high-pressure mercury lamp is used, the exposure process uses, for example, 500 mJ/cm²) Or a light dose of less than 500 mj/cm (using a 365 nm sensor). However, the light dose may vary depending on the kind of each component of the curable composition, the combination ratio thereof, and the dry film thickness.

(3) Development

After the exposure process, the exposed film is developed by dissolving and removing an unnecessary portion except for the exposed portion using an alkaline aqueous solution to form an image pattern. In other words, when developed using an alkaline developing solution, the unexposed area is dissolved and an image color filter pattern is formed.

(4) Post-treatment

The developed image pattern may be cured again by heating or irradiation with actinic rays or the like to achieve excellent qualities in terms of heat resistance, light resistance, close contact property, crack resistance, chemical resistance, high strength, storage stability and the like.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention is described in more detail with reference to examples. However, these examples should not be construed in any way as limiting the scope of the invention.

(Synthesis of ligand)

Synthesis example 1

400 g of Polyoxyethylene Monomethyl Ether (Polyoxylene monomethylether) (MPEG-400, Hannong Chemicals Inc.), 124 g of Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride), 500 g of toluene (tolene) and 60 g of triethyleneamine (triethyleneamine) were placed, and then heated to 100 ℃ and reacted for 24 hours. When the reaction was completed, the resultant was neutralized with 5% aqueous HCl solution, and toluene (tolumen) was removed therefrom to obtain 500 g of a final product represented by chemical formula 1-1A.

[ chemical formula 1-1A ]

Synthesis example 2

400 g of a final product represented by chemical formula 1-2A was obtained in the same manner as in Synthesis example 1, except that 270 g of Polyoxyethylene phenyl Ether (Polyoxylene phenyl Ether) (PH-4, Han nong chemical Co., Ltd.) was used in place of 400 g of Polyoxyethylene Monomethyl Ether (Polyoxylene monomethylene Ether).

[ chemical formula 1-2A ]

Synthesis example 3

630 g of the final product represented by chemical formulas 1 to 3 was obtained according to the same method as in synthetic example 1, except that 520 g of polyoxyethylene cumyl phenyl ether (hannong chemical company) was used instead of 400 g of polyoxyethylene monomethyl ether.

[ chemical formulas 1-3A ]

Comparative Synthesis example 1

10 g of 2-mercapto-1-ethanol (2-mercapto-1-ethanol), 13.3 g of 2-2- (2-methoxyethoxy) ethoxyacetic acid (2-2- (2-methoxyethoxy) ethoxyacetic acid) and 2.1 g of p-toluenesulfonic acid monohydrate (p-toluenesulfonic acid monohydrate) were placed in a 2-neck round-bottom flask, and then dissolved in 300 ml of cyclohexane (cyclohexane). Dean stark was fastened into the injection hole and a condenser (condensor) was connected thereto. After the reaction was refluxed for 8 hours, the reaction was complete. (the final amount of water collected in dean stark was measured). The reaction was transferred to a separatory funnel (Separating funnel), and then subjected to extraction (extraction), neutralization to remove the solvent, and drying in a vacuum oven to obtain a final product represented by chemical formula C-1.

[ chemical formula C-1]

(preparation of a Dispersion of Quantum dots surface-modified with ligands)

Preparation example 1

After the magnetic rod was put into the 3-neck round-bottom flask, a quantum dot-cyclohexyl acetate (CHA) solution (solid content: 26 wt% to 27 wt%) was measured and put therein. To which a ligand represented by chemical formula 1-1 is added.

The resultant was thoroughly mixed for 1 minute, and then stirred at 80 ℃ under a nitrogen atmosphere. When the reaction was completed, the resultant was cooled (firing) to room temperature, and the quantum dot reaction solution was added to cyclohexane (cyclohexane) to obtain a precipitate. The precipitated quantum dot powder was separated from cyclohexane (cyclohexane) by centrifugation. The clear solution was decanted and discarded, and the precipitate was then dried in a vacuum oven thoroughly for one day to obtain surface-modified quantum dots.

The surface-modified quantum dot was stirred with a monomer represented by chemical formula 3-2 (1,6-hexanediol diacrylate); Miwon Commercial Co., Ltd.) for 12 hours to obtain a surface-modified quantum dot dispersion.

[ chemical formula 3-2]

Preparation example 2

A surface-modified quantum dot dispersion was obtained according to the same method as preparation example 1, except that the ligand represented by chemical formula 1-2 was used instead of the ligand represented by chemical formula 1-1.

Preparation example 3

A surface-modified quantum dot dispersion was obtained according to the same method as preparation example 1, except that the ligand represented by chemical formula 1-3 was used instead of the ligand represented by chemical formula 1-1.

Comparative preparation example 1

A surface-modified quantum dot dispersion was obtained according to the same method as preparation example 1, except that the ligand represented by chemical formula C-1 was used instead of the ligand represented by chemical formula 1-1.

Evaluation 1: dispersibility

The Particle Size of each of the quantum dot dispersions according to preparation examples 1 to 3 and comparative preparation example 1 was measured three times with a Particle Size Analyzer (Particle Size Analyzer) by using a Micro Particle Size Analyzer (Micro Particle Size Analyzer) to obtain an average Particle Size, and the results are shown in table 1.

(Table 1)

Particle size (nm)	Preparation example 1	Preparation example 2	Preparation example 3	Comparative preparation example 1
					D50	11.0	11.2	11.8	15.0

From table 1, each of the quantum dot dispersions according to preparation examples 1 to 4 showed a narrow particle distribution, which indicates that the quantum dots are well dispersed in the high boiling point and high surface tension solvent, but the quantum dot dispersion according to comparative preparation example 1 showed a broad particle distribution, which indicates that the quantum dots are not well dispersed in the high boiling point and high surface tension solvent.

(preparation of solvent-free curable composition)

Example 1

The dispersion according to preparation example 1 was weighed and then mixed with the monomer represented by Chemical formula 3-2 and diluted, and a polymerization inhibitor (methyl hydroquinone, Tokyo Chemical Industry co., Ltd.) was added thereto, and then stirred for 5 minutes. Subsequently, a photoinitiator (TPO-L,polynetron) and to which a light diffuser (TiO) is added₂(solids: 50% by weight); ditto Technology co, Ltd.)). The entire dispersion was stirred for 1 hour to prepare a solvent-free curable composition. The quantum dot is included in an amount of 40 wt%, the monomer represented by chemical formula 3-2 is included in an amount of 48 wt%, the polymerization inhibitor is included in an amount of 1 wt%, the photo initiator is included in an amount of 3 wt%, and the light diffuser is included in an amount of 8 wt%, based on the total amount of the solvent-free curable composition.

Example 2

A solvent-free curable composition was prepared according to the same method as example 1, except that the dispersion according to preparation example 2 was used instead of the dispersion according to preparation example 1.

Example 3

A solvent-free curable composition was prepared according to the same method as in example 1, except that the dispersion according to preparation example 3 was used instead of the dispersion according to preparation example 1.

Comparative example 1

A solvent-free curable composition was prepared according to the same method as example 1, except that the dispersion according to comparative preparation example 1 was used instead of the dispersion according to preparation example 1.

Evaluation 2: evaluation of optical Properties

Each of the solvent-free curable compositions according to examples 1 to 3 and comparative example 1 was coated to a thickness of 15 μm on a Yellow Photoresist (YPR) with a spin coater (800 revolutions per minute (rpm), 5 seconds, oppoki kott (optical) MS-a150, sank limited (Mikasa co., Ltd.), and exposed to 5000 millijoules (mJ) with a 395 nm Ultraviolet (UV) exposure machine under a nitrogen atmosphere (83 ℃, 10 seconds). Subsequently, single film samples of 2 centimeters (cm) by 2 centimeters each were loaded in an integrating sphere device (QE-2100, tsukamur Electronics, Ltd.) to measure light conversion rates. Then, the loaded single film sample was dried in a drying oven at 180 ℃ for 30 minutes under a nitrogen atmosphere, and then, the light retention of the sample after exposure to drying was measured, and the results are shown in table 2.

(Table 2)

	Light conversion Rate (%)	Light holding ratio (%)	Maximum emission wavelength (nm)
				Example 1	27.3	92	542
Example 2	28.1	93	542
				Example 3	26.2	91	542
Comparative example 1	22.8	91	543

From table 2, the solvent-free curable compositions according to the examples showed improved optical properties.

(preparation of solvent-type curable composition)

Example 4

The following components were used in corresponding amounts to prepare solvent-type curable compositions (photosensitive resin compositions).

Specifically, a photopolymerization initiator was dissolved in a solvent, and then sufficiently stirred at room temperature for 2 hours. Subsequently, a binder resin was added thereto together with the quantum dot dispersion of preparation example 1, a dispersant (dego (TEGO) D685, winning company (Evonik Corp.)) and a polymerizable monomer, and then stirred at room temperature for 2 hours again. Then, a light diffusing agent and a fluorine-based surfactant were added thereto, and then stirred at room temperature for 1 hour, and the above product was filtered three times to remove impurities and thus prepare a photosensitive resin composition.

1) Quantum dot dispersion: preparation example 1

2) Binder resin: 25% by weight of Casino multisystem adhesive resin (TSR-TA01, Takema (TAKOMA))

3) Polymerizable monomers: 5.4% by weight of pentaerythritol hexamethylacrylate (DPHA, Nippon Kayaku Co., Ltd.)

4) Photopolymerization initiator: 0.7 wt% of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide (TPO, Sigma-Aldrich Corporation)

5) Solvent: 39% by weight dimethyl adipate (dimethyl adipate)

6) Light diffusing agent: 15% by weight of a titanium dioxide dispersion (TiO)₂Solid content: 20 wt%, average particle diameter: 200 nm, Dituo Technique Co Ltd

7) Other additives: 0.9% by weight of a fluorine-based surfactant (F-554, Dainippon ink chemical Co., Ltd.)

Example 5

A photosensitive resin composition was obtained according to the same method as example 4, except that the quantum dot dispersion of preparation example 2 was used instead of the quantum dot dispersion of preparation example 1.

Example 6

A photosensitive resin composition was obtained according to the same method as example 4, except that the quantum dot dispersion of preparation example 3 was used instead of the quantum dot dispersion of preparation example 1.

Comparative example 2

A photosensitive resin composition was obtained according to the same method as example 4, except that the quantum dot dispersion of comparative preparation example 1 was used instead of the quantum dot dispersion of preparation example 1.

Evaluation 3: light conversion rate and light retention rate of quantum dots

The curable compositions according to examples 4 to 6 and comparative example 2 were coated to a thickness of 6 μm on a single surface of a glass substrate respectively using a spin coater (150 revolutions per minute (rpm), opu (optical) MS-a150, chimpanzee (Mikasa) ltd), and then dried on a hot plate (hot-plate) of a hot plate (hot-plate) at 80 ℃ for 1 minute to obtain a film. Then, the power consumption (power) was 100 mJ/cm²) After the ultraviolet irradiation, the light conversion rate was measured with an exposure machine (ghi broadband, Ushio Inc.) by performing post-baking (POB) in a convection cleaning oven (Jongro) at 180 ℃ for 30 minutes, and the results are shown in table 3.

(Table 3)

(unit:%)

	Example 4	Example 5	Example 6	Comparative example 2
					Initial light conversion ratio	24.6	26.0	23.9	22.0
Optical conversion ratio after POB is performed once	24.3	25.2	23.1	20.0

As shown in table 3, the solvent-type curable composition prepared by using the surface-modified quantum dots according to the example exhibited small deterioration of light conversion rate due to the color filtering process, but exhibited high light retention rate.

While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, it should be understood that the above-described embodiments are exemplary, and are not to be construed as limiting the invention in any way.

Claims

1. A quantum dot surface-modified with a compound represented by chemical formula 1:

[ chemical formula 1]

Wherein, in chemical formula 1,

l is a divalent moiety derived from an acid dianhydride,

L¹and L²Independently a substituted or unsubstituted C1 to C20 alkylene,

m is an integer of 1 to 20.

2. The quantum dot of claim 1, wherein the L is a divalent moiety derived from a compound represented by one of chemical formulas 2-1 to 2-15:

[ chemical formula 2-1]

[ chemical formula 2-2]

[ chemical formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

[ chemical formulas 2 to 6]

[ chemical formulae 2 to 7]

[ chemical formulas 2 to 8]

[ chemical formulas 2 to 9]

[ chemical formulas 2-10]

[ chemical formulas 2 to 11]

[ chemical formulas 2-12]

[ chemical formulas 2-13]

[ chemical formulae 2 to 14]

[ chemical formulas 2 to 15]

3. The quantum dot of claim 1, wherein the L is represented by one selected from group 1:

[ group 1]

4. The quantum dot of claim 1, wherein chemical formula 1 is represented by one of chemical formula 1-1 to chemical formula 1-3:

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

Wherein, in chemical formulas 1-1 to 1-3,

n is an integer of 1 to 20.

5. The quantum dot of claim 1, wherein the quantum dot has a maximum fluorescence emission wavelength of 500 to 680 nanometers.

6. A solvent-free curable composition comprising

The quantum dot of claim 1; and

a polymerizable monomer having a carbon-carbon double bond at a terminal.

7. The solvent-free curable composition according to claim 6, wherein the polymerizable monomer has a molecular weight of 220 g/mole to 1,000 g/mole.

8. The solvent-free curable composition according to claim 6, wherein the polymerizable monomer is represented by chemical formula 3:

[ chemical formula 3]

Wherein, in chemical formula 3,

L⁸is a substituted or unsubstituted C1 to C10 alkylene or ether (— O-).

9. The solvent-free curable composition of claim 6 comprising

1 to 60% by weight of the quantum dots, and

40 to 99 weight percent of the polymerizable monomer.

10. The solvent-free curable composition of claim 6, further comprising a polymerization initiator, a light diffuser, or a combination thereof.

11. A solvent-borne curable composition comprising:

the quantum dot of claim 1;

a binder resin; and

a solvent.

12. The solvent-borne curable composition of claim 11, comprising

1 to 40 weight percent of the quantum dots;

1 to 30% by weight of the binder resin; and

the balance of the solvent.

13. The solvent-borne curable composition of claim 11, further comprising a polymerizable monomer, a polymerization initiator, a light diffuser, or a combination thereof.

14. A cured layer produced using the solvent-free curable composition of claim 6.

15. A color filter comprising the cured layer of claim 14.